Process for producing methane from gas streams containing carbon monoxide and hydrogen

ABSTRACT

Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO 2 , from which a relatively pure methane product may be obtained. While carbon monoxide-containing gas streams having hydrogen or water present therein can be used only the carbon monoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H 2  -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.

STATEMENT

The Government of the United States of America has rights pursuant to Contract No. ET-78-C-03-2153 awarded by the Department of Energy.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the production of methane from carbon monoxide. More particularly, it relates to a methanation process capable of effectively utilizing dilute carbon monoxide-containing gas streams also containing appreciable quantities of hydrogen.

2. Description of the Prior Art

The catalytic hydrogenation of carbon monoxide to form methane is one of the most well known and established hydrogenation reactions. This reaction, which is:

    CO+3H.sub.2 →CH.sub.4 +H.sub.2 O,                   (1)

utilizes a synthesis gas, as from the gasification of coal with oxygen and steam, that is treated to provide a desired H₂ /CO ratio and to remove excess CO₂ and deleterious impurities such as sulfur compounds. As the H₂ /CO ratio of the raw synthesis gas is substantially below the necessary minimum ratio of 3/1, at least a portion of the carbon monoxide in the gas is generally first reacted with steam, over an iron or other suitable catalyst in the well-known "water shift" reaction, as follows:

    CO+H.sub.2 O→CO.sub.2 +H.sub.2.                     (2)

Excess CO₂ in the gas stream is removed by conventional means, such as by treatment with alkaline absorbents. Sulfur impurities are also removed to substantially under 5 ppm, e.g., to less than about 1 ppm, preferably to less than 0.2 ppm, to protect the methanation catalyst from poisoning by such sulfur impurities.

The water shift reaction normally does not go to completion, with the equilibrium determined by the reaction temperature and other operating conditions limiting the degree of completeness of the reaction. The desired H₂ /CO ratio is obtained, to achieve maximum utilization of the available CO and hydrogen, either by very careful choice and control of the processing conditions or by the treatment of a portion of the raw synthesis gas to produce a H₂ /CO ratio substantially in excess of 3/1 and blending the treated gas with the untreated portion to produce the desired H₂ /CO ratio.

One variation of the latter approach is disclosed in the Muller patent, U.S. Pat. No. 3,854,895, in which the primary gas from coal gasification is divided into two streams, one of which is subjected to water shift and subsequent methanation stages, the untreated stream being added to said treated gas successively during said methanation stages. Numerous prior art techniques also exist, it should be noted, for the production of methane from other gases containing hydrogen and carbon oxides. Humphries et al, U.S. Pat. No. 3,511,624, for example, relates to the two-stage production of a gas containing a high proportion of methane from a reaction mixture comprising hydrogen, carbon monoxide and dioxide, steam and at least 25% by volume methane.

Despite the established nature of the major steps in the known techniques for the gasification of coal and in the methanation of the resulting synthesis gas, improved processes for the production of methane are urgently needed to enhance the overall economics of methane production and/or to enable its production from carbon-monoxide-containing gas streams that cannot presently be used in a commercially feasible manner for the production of methane. This need is highlighted by the diminishing supply of natural gas and the recognized need to develop economical supplies of synthetic natural gas to meet existing and anticipated requirements for low-cost, high BTU gaseous heating fuels.

In the processing of synthesis gas obtained by the gasification of coal with oxygen and steam, pretreatment by the catalytic water shift reaction is a major processing step prior to methanation. This necessary adjustment of the H₂ /CO ratio adds, of course, to the overall processing costs and necessarily reduces the amount of carbon monoxide available for conversion to methane. In addition, gas streams containing a low concentration of carbon monoxide and/or a high concentration of inert gases are generally not suitable for methanation purposes because of the costs associated with the concentration of the carbon monoxide, as by cryogenic or absorption means. For example, the effluent from the underground gasification of coal with air is not a suitable feed gas for conventional methanation techniques because of the high proportion of inert gases, i.e., nitrogen, in said effluent. Similarly, the effluent from blast furnace operations contains a high proportion of nitrogen and is not suitable for the economic production of methane because of the prohibitive cost of concentration of the carbon monoxide content thereof.

Conventional processing techniques, in addition, are known to have particular operating difficulties, the overcoming to which tends to shift the equilibrium and reduce the yield of desired methane product or tends to reduce the overall efficiency of the production reaction. The Muller patent referred to above, i.e., U.S. Pat. No. 3,854,895, thus discloses that the formation of free carbon by the Boudouard reaction is promoted by an increase of CO in the reaction mixture, leading the prior art to employ excess hydrogen and to obtain not pure methane but a mixture of methane and hydrogen. The above-mentioned Humphries et al patent, U.S. Pat. No. 3,511,624, likewise refers to said Boudouard reaction:

    2CO→CO.sub.2 +C                                     (3)

and discloses the known use of steam to react with a portion of the CO in the gas stream per reaction (2) above to assure the presence of sufficient CO₂ to prevent the Boudouard reaction from moving to the right and causing carbon deposition, the process including the removal of the resulting carbon dioxide and any remaining steam from the mixture. While the problem of undesired carbon deposition is thus avoided in the art, the necessary adjustments to achieve this result create a further incremental limitation on the processing economy and flexibility of the prior art techniques for methane production. For practical commercial operations, it is highly desirable in the art that, without such limitations, a methanation process be developed that can be operated on a continuous cyclic basis without undue loss of catalyst efficiency and without a need for continuous catalyst regeneration as a necessary step of the cyclic methanation process.

It is an object of the invention, therefore, to provide an improved process for the production of methane.

It is another object of the invention to provide a process for the low-cost production of methane from carbon monoxide-containing gas streams.

It is another object of the invention to provide a process for the production of methane from dilute carbon monoxide-containing gas streams without the necessity for preliminary concentration of the carbon monoxide in said gas streams.

It is another object of the invention to provide a process for the enhanced catalytic production of methane from carbon monoxide-containing gas streams on a cyclic basis without requiring catalyst regeneration as a necessary step of the cyclic process.

With these and other objects in mind, the invention is hereinafter described in detail, the novel features thereof being particularly pointed out in the appended claims.

SUMMARY OF THE INVENTION

The process of the invention employs partial oxidation to selectively remove hydrogen from a CO-containing gas stream followed by the catalytic disproportionation of said carbon monoxide to carbon and carbon dioxide to deposit a surface layer of active surface carbon on the surface of a catalyst, at about 100°-400° C. and 1-100 atmos., essentially without the subsequent formation of inactive coke thereon. The layer of active surface carbon is thereafter contacted with steam, at about 100°-400° C. and 1-100 atmos., thus converting the active surface carbon to methane and carbon dioxide. In a less desirable embodiment, the surface layer may be contacted with hydrogen rather than with steam. No concentration of carbon monoxide and/or separation of inert gases is required prior to the use of dilute carbon monoxide-containing streams except for the preliminary removal of hydrogen by the partial oxidation thereof. At least about 12.5% and up to nearly 25% of the carbon in said carbon monoxide decomposed on the catalyst is recovered in the form of relatively pure methane. By carrying out the conversion of active surface carbon with high pressure steam, a product stream of high pressure, relatively pure methane is produced without the necessity for employing expensive compression equipment and incurring a large consumption of energy for compressive purposes. For enhanced methanation in practical commercial operations, a cyclic, essentially two-step process is desirable, with the disproportionation catalyst being employed in such cyclic, two-step operations without the need for regenerating the catalyst as a necessary additional step of the cyclic process. Especially preferred catalysts for such cyclic operations are nickel, cobalt, ruthenium, rhenium and alloys thereof, in the metal state. For practical commercial operations, it is especially preferred that, following preliminary partial oxidation for hydrogen removal from the CO-containing gas stream, the CO disproportionation step be carried out at temperatures of from about 200° C. up to about 350° C., and that the active surface carbon deposited on the catalyst be reacted with steam for conversion to produce methane and carbon dioxide.

DETAILED DESCRIPTION OF THE INVENTION

The invention enables dilute carbon monoxide containing gas streams, unacceptable for use by known processes, to be effectively and efficiently utilized for the economic production of methane. Such utilization is enhanced by the selective removal of hydrogen from the gas stream prior to methanation. Separation of the carbon monoxide from inert gases present in such dilute carbon monoxide-containing streams is accomplished, in the practice of the present invention, without economic disadvantage vis-a-vis known processes applicable to carbon monoxide-containing gas streams not containing appreciable quantities of inert gases. The present invention is of significance, therefore, not only as a process for the production of low-cost methane but as a process uniquely capable of utilizing carbon monoxide available in gas streams not previously suitable as feed streams for the commercial production of methane.

The invention includes the passing of a carbon monoxide-containing gas stream, after preliminary removal of hydrogen as herein disclosed and claimed, over a suitable catalyst under conditions such that the carbon monoxide is decomposed to form carbon dioxide and active surface carbon, designated as C* and deposited as a surface layer on said catalyst, according to the reaction:

    2CO→CO.sub.2 +C*.                                   (4)

The carbon dioxide and inert gases present in the feed stream are vented from the surface layer of active surface carbon, which is thereafter converted to methane by contact with steam as follows:

    2C*+2H.sub.2 O→CH.sub.4 +CO.sub.2.                  (5)

The carbon efficiency of the process can be illustrated by the overall reaction (6) below that represents the total of reactions (4) and (5) as performed in the practice of the present invention:

    4CO+2H.sub.2 O→3CO.sub.2 +CH.sub.4.                 (6)

Thus, 4 moles of CO are required for the production of one mole of methane in the stoichiometric relationship illustrated by reaction (6). The present invention is capable of recovering methane in amounts representing at least about 50% of the stoichiometric amount and, in preferred embodiments, at least about 80% and up to nearly 100% of said stoichiometric amount. Upon separation from the accompanying CO₂ by conventional means, therefore, methane is recovered in the form of a low-cost, relatively pure product with the carbon values thus recovered being at least about 12.5% and up to nearly 25% of the carbon present in the carbon monoxide decomposed upon contact with the disproportionation catalyst.

Gas streams containing from about 1 to nearly 100% by volume carbon monoxide, but with an appreciable amount of hydrogen therein, can be utilized as the feed stream in the practice of the invention. As indicated above, the invention is uniquely capable of utilizing carbon monoxide in gas streams not suitable for known methanation techniques because of relatively high concentrations of inert gases therein. Gas streams containing carbon monoxide in amounts of from about 5% to about 50% by volume and containing at least about 5% by volume of nitrogen, together with said appreciable amount of hydrogen, represent sources of carbon monoxide not previously suitable for commercial methanation operations that are highly suitable for use in the process of the invention. Those skilled in the art will readily appreciate that the gas streams should be sufficiently free from catalyst poisons to ensure adequate catalyst lifetimes. Thus, sulfur impurities should be present in very low concentrations, e.g. less than 1 ppm, preferably less than 0.2 ppm. Conventional techniques not forming a part of this invention are available in the art for removing sulfur impurities as required. Apart from hydrogen removal as herein provided and dehydration, water vapor present in the feed gas stream may be converted, partially or completely, to methane by reaction with carbon monoxide under the reaction conditions. The carbon monoxide remaining after said reaction with any such hydrogen or water vapor will be decomposed to active surface carbon and carbon dioxide in accordance with reaction (4) above. For this reason, the hydrogen and water vapor present in the feed gas stream to the disproportionation reaction will desirably contain less than 10% by volume of the amount of carbon monoxide present in the gas stream. While any methane formed during the carbon monoxide decomposition step, because of the presence of hydrogen or water vapor, may be utilized for heat generation purposes enhancing the overall economics of the subject low-cost methanation process, such processing is not generally desired, at least in part because of the temperature control problems inherent as a result of the methanation reaction when occuring during the disproportionation step of the process.

When the feed gas for the subject cyclic methanation process contains appreciable quantities of hydrogen in addition to the desired carbon monoxide, it is thus desirable to remove hydrogen therefrom in a pretreatment step so as to avoid undesired methanation during the CO disproportionation step. For this purpose, the feed gas stream, after sulfur removal, if required, and the addition of sufficient steam to suppress coking, may be passed to a methanation zone maintained, e.g. at 600+° F. for consumption of said hydrogen via reaction (1) above. This approach results in a loss of one mole of CO for every three moles of hydrogen consumed, and also requires the addition of a methanation zone containing relatively costly and sensitive methanation catalyst. It is desirable to obviate the need for such additional methanation zone, therefore, to improve the overall technical and economic attractiveness of the subject cyclic methanation process.

In the practice of the present invention, feed streams containing appreciable quantities of hydrogen in addition to the desired carbon monoxide are preheated so as to preferentially remove hydrogen from such feed gas streams. For this purpose, the CO/H₂ feed gas stream is passed to a partial oxidation reaction zone for contact with air thereof to selectively oxidize the hydrogen content thereof in preference to the carbon monoxide content of the feed gas present in the reaction mixture. Air or other oxygen-containing gas is employed in said reaction zone in an amount determined by the H₂ and CO content of the feed gas, e.g. based on 100% H₂ removal and oxidation of up to 33% of the CO. The resulting total partial pressure of H₂ and O₂ dictates the safe, optimum furnace temperature for operation within the tolerable limits for non-explosive reaction. The resulting pretreated CO-containing gas stream having hydrogen preferentially removed therefrom is desirably passed to a dehydration zone for the removal of water vapor. The feed gas removed from said zone can then be passed over the catalyst employed in the cyclic methanation process for the conversion of CO to methane. It will be understood by those skilled in the art that sulfur impurities that may be present in the feed gas stream are advantageously removed therefrom prior to passage of the feed gas to the partial oxidation reaction zone of the invention. If a significant amount of CO S is present, for example, the feed gas may be passed, e.g. at 400° F., through a hydrolysis reactor for conversion to H₂ S. The feed gas may then be cooled and passed through an aqueous amine scrubber or other conventional solvent to remove most of the H₂ S, which can advantageously be sent to a Claus unit for conversion to sulfur as is well known in the art. The thus-scrubbed feed gas can thereafter be reheated and passed, for example, through a ZnO guard bed to lower the H₂ S content to a very low concentration prior to passage to the partial oxidation zone for preferential oxidation of the hydrogen content of the feed gas. If, however, SO₂ forms and remains the dominant species under the partial oxidation conditions, as would be expected, and if the disproportionation catalyst is reasonably impervious to relatively low concentrations of SO₂ , then the inclusion of such a ZnO guard bed, or like means such as iron oxide or activated carbon, may not be required in the preparation of the feed gas for use in the process of the invention.

With respect to the partial oxidation step of the invention, it should be noted that the reaction of hydrogen and oxygen gases has been the subject of work reported in the literature that serves to define the explosive limits of such hydrogen and oxygen mixtures. Thus, B. Lewis and G. Vonelbe, "Combustion, Flames and Explosions of Gases", pp. 3-89, Academic Press, New York, San Francisco, London, Second Edition, 1961, at p. 24 shows, in FIG. 1 thereof, the explosive limits of a stoichiometric hydrogen-oxygen mixture. On pp. 53 thereof, FIG. 13 discloses curves of equal reaction rates for the hydrogen-oxygen reaction at various temperature and pressure conditions up to the experimental explosion limit of such reaction mixtures. Such disclosure is incorporated herein by reference and serves to illustrate the practical limits for the partial oxidation step of the invention employed in the pretreatment of CO and H₂ containing gas streams as herein disclosed and claimed.

In the art, work has also been carried out to study the combustion of CO/H₂ mixtures. E. J. Buckler and R. G. W. Norrish, Proc. Roy. Soc. (London) A167, 292, 318 (1938), on p. 320 thereof, report the oxidation of hydrogen in CO/H₂ /O₂ mixtures outside the explosive limits thereof as noted in the course of studies intended to define such explosive limits. The observed selective oxidation of a significant fraction of hydrogen during the manipulation of the gases for the intended purpose was treated as a hindrance to be overcome in such work.

The invention provides a unique and advantageous processing technique for selectively removing hydrogen from the feed gas stream so as to enhance the active carbon deposition step and the overall effeciency of the subject cyclic, essentially two-step methanation process. The invention obviates the need for employing a catalytic methanation zone to achieve desirable hydrogen removal from said feed stream. Thus, the use of a partial oxidation reaction zone, and the operation of said zone with the practical limits for non-explosive reaction of a hydrogen-oxygen mixture, as defined by the prior art studies referred to above, the hydrogen content is found to be selectively oxidized and removed from the feed gas. In this regard, it will be understood that the non-explosive limits for the CO/H₂ /O₂ reaction mixture within the partial oxidation zone of the invention approximates the non-explosive limits for the stoichiometric hydrogen-oxygen mixtures of the prior art studies. As will be appreciated from a review of said prior art studies, the explosive limits of said mixtures of hydrogen and oxygen define a non-explosive region or peninsula within which the selective oxidation of hydrogen can be carried out in safe, practical commercial operation of the subject process. The amount of air or other oxygen-containing gas employed in said partial oxidation reaction zone will thus be limited so that, at the particular temperature and pressure employed in said zone, the total partial pressure of hydrogen and oxygen in the reaction mixture is within the limits for non-explosive reaction of homogeneous mixtures of said hydrogen and oxygen at said reaction conditions.

The prior art studies pertaining to stoichiometric reaction mixtures of hydrogen and oxygen, as referred to above and incorporated herein by reference, establish that increased temperature and pressure of the reaction mixture enhance the rate of reaction within the limits for non-explosive reaction. It is generally desirable, therefore, to operate as close to the tip of the non-explosive region or peninsula as possible and practical without passing into the explosion region of operating conditions. On FIG. 1 on p. 24 of the Lewis and Vonelbe report referred to above, it will be seen that the partial oxidation zone is desirably operated so that the reaction is carried out at a temperature of from about 540° C. to about 575° C., although temperatures outside such range can also be employed so long as the reaction is carried out in the non-explosion region.

While the partial oxidation reaction can likewise be carried out at any desired pressure remaining within the non-explosion range, there is no particular advantage to the use of pressures above those that may be desirable to achieve an appropriate pressure differential in the system. Accordingly, reaction pressures of from about one to about two atmospheres are generally preferred for the partial oxidation reaction zone although pressures outside this range may also be employed.

Those skilled in the art will appreciate that the selective removal of hydrogen, as herein disclosed and claimed, may advantageously be employed as a pretreatment step of the subject process whenever appreciable quantities of hydrogen are present in the feed stream. For purposes of this invention, it will be understood that appreciable quantities of hydrogen shall include any amount of hydrogen that will react in the active carbon deposition step to form methane in such quantities as to adversely affect the efficiency and effectiveness of the subject cyclic methanation process. It is within the scope of the invention, therefore, to utilize the partial oxidation step herein disclosed and claimed for the removal or relatively small amounts of hydrogen or to pretreat a stream containing quite large amounts of hydrogen in addition to the carbon monoxide content to be converted to methane. The hydrogen content of the feed gas to be treated may thus be either less or greater than the carbon monoxide content thereof. Those skilled in the art will appreciate, however, that a trade-off of various processing factors will determine the practical desirability of utilizing the subject partial oxidation pretreatment step in preference to permitting the hydrogen to remain in the feed stream to the disproportionation step or the alternative of employing a catalytic methanation zone for hydrogen removal in any given application of the cyclic, two-step methanation process. In the practice of the invention, the partial oxidation can be operated under such carefully controlled conditions as to insure almost complete oxidation of the hydrogen in the feed stream. The particular combination of temperature, pressure, reaction rate and the like to achieve such result will depend, of course, on the composition of the feed gas, the type of partial oxidation reaction zone employed and the interrelationship of such factors with the need to remain within the non-explosive range of H₂ /O₂ mixtures as established heretofore in the art. It will be appreciated that the selective removal of hydrogen as herein provided does not imply that no carbon monoxide is consumed in the partial oxidation zone. While the partial oxidation reaction selectively removes hydrogen, up to about 35% of the carbon monoxide will be removed together with the hydrogen in those instances where approximately equal portions of H₂ and CO are in the feed gas being treated. The amount of CO consumed will likewise vary depending on the various processing factors involved in any given application. It will be seen that the loss of CO in the practice of the subject partial oxidation process may be on the order of that occurring as a result of methanation reaction (1) above, namely one mole of CO for every three moles of hydrogen consumed when methanation occurs during the disproportionation step or in a pretreatment utilizing a separate catalytic methanation zone. In such instance, the present invention nevertheless has the practical advantage of avoiding the relatively costly use of methanation catalyst in the pretreatment step and/or avoiding the heat control problems resulting from appreciable methanation during the disproportionation step. The invention thereby provides a useful improvement further enhancing the flexibility, efficiency and effectiveness of the subject cyclic methanation process as applied to CO-containing gas streams suitable as feed gas to said process. One such commercially available CO-containing gas stream suitable for the practice of the invention is carbon black tail gas, which typically contains on the order of about 8% CO, 8% H₂, 2% CO₂, 32% N₂ and 50% water vapor. As the hydrogen and water vapor content thereof will react with the active carbon species as formed during the disproportionation step, such components as present in the tail gas are advantageously removed by the partial oxidation pretreatment step of the invention, in addition to conventional H₂ S removal, prior to passing to the disproportionation reaction zone.

The partial oxidation pretreatment step of the invention will be carried out in a suitable oxidation furnace, the type of which will depend upon the operating conditions employed in any given application. For operations close to the explosive limits of the CO/H₂ /O₂ reaction mixture, i.e. close to the explosive limits of a H₂ /CO mixtu mixture, the reaction rates would be relatively fast, so that a fluidized bed furnace would be advantageous for dampening local temperature excursions that might otherwise be more costly or difficult to control to within the desired non-explosive operating range. When operating in processing regions further removed from the explosive limits, on the other hand, the reaction rates are generally slower, and an oxidation furnace having a longer gas residence time would be appropriate. The latter type of furnace might, for example, conveniently be a highly turbulent gas furnace or a plug flow tubular furnace of conventional design.

It is within the scope of the invention to utilize the partial oxidation pretreatment step, under appropriate conditions for any particular application, to achieve essentially complete oxidation of the hydrogen content of the feed gas or to achieve selective removal of a portion of the hydrogen content, thereby diminishing the amount of hydrogen available for methanation during the disproportionation step. It will be appreciated that the hydrogen remaining in the feed gas passed to the disproportionation step, together with any water vapor not removed by dehydration of the pretreated feed gas in a glycol scrubber or other dehydration zone, will be converted to methane during the disproportionation step. Such resulting methane will be vented from the catalyst having active surface carbon deposited thereon together with the carbon dioxide and inert gases present in the by-product gas stream removed from the disproportionation catalyst. The vented methane can be fed to a combustion zone for combustion therein for heat generation purposes. The resulting heat can be used, for example, in the generation of steam, such as that employed to convert the active surface carbon to product methane. A combination of partial oxidation for appreciable hydrogen removal, with such use of vented methane from residual amounts of hydrogen and water vapor in the feed gas stream, will be understood to be included within the scope of the invention.

The carbon monoxide decomposition step, in which the carbon monoxide present in the pretreated feed gas stream is decomposed to form a surface layer of active surface carbon despoited on a disproportionation catalyst, effectively serves to concentrate the carbon values to be converted to methane, regardless of the carbon monoxide content of the feed gas stream. Dilute carbon monoxide-containing gas streams can be readily employed, therefore, without the necessity for the prior concentration of the carbon monoxide as would be required in conventional techniques apart from desirable removal of hydrogen therefrom in the pretreatment step of the invention. The venting of the carbon dioxide formed as a result of carbon monoxide decomposition, together with the inert gases that may be present in the gas stream, from the catalyst having surface layer of active surface carbon values to be converted to methane from said gases, is readily carried out as an incidental unit operation procedure prior to said active surface carbon conversion in the second chemical step of the essentially two-step cyclic methanation process carried out after pretreatment of the feed gas for hydrogen removal purposes. The use of a dilute carbon monoxide-containing gas stream in the process of the invention thus does not require the prior separation of the carbon monoxide content thereof from such inert gases, as would be required in conventional methanation techniques. This ability to utilize dilute carbon monoxide-containing gas streams constitutes a major advance in the art, permitting the production of low-cost methane from gas streams not capable of practical utilization for the economic production of methane by presently available techniques.

The decomposition of carbon monoxide over a disproportionation catalyst is carried out at a reaction pressure of from about 1 to about 100 atmospheres and at a reaction temperature of from about 100° C. to about 400° C., preferably between about 200° C. and about 300° C. with space velocities of from about 1000 to about 30,000 hr⁻¹. Since the most useful product of the carbon monoxide decomposition, for purposes of the cyclic methanation process of the invention is the solid surface layer of active surface carbons, it will usually be of no advantage to carry out the decomposition reaction at pressures much above atmospheric. The pretreated carbon monoxide-containing gas stream is passed over the catalyst for a time sufficient to deposit a surface layer of active surface carbon on the catalyst essentially without the formation of inactive coke thereon. Such inactive coke is not only itself inert under the methanation reaction conditions of the invention, but may tend to reduce the capacity of the catalyst to form active surface carbon in subsequent operations. For practical commercial applications, such subsequent operations, involving the use of the catalyst for the disproportionation of additional quantities of CO, are desirably carried out at reaction temperatures above about 100° C. and preferably within said preferred range of from about 200° C. to about 300° C. or even higher up to about 350° C. It will be understood that said CO disproportionation temperature refers to the average temperature refers to the average temperature of the reaction bed. It will also be understood by those skilled in the art that the particular reaction temperature pertaining to any given commercial application of the invention will be subject to inevitable variations depending on the type of operation employed, e.g. fixed or fluid bed, and on the capability of temperature control equipment employed in such commercial application of the invention. The reaction temperature may exceed the indicated preferred temperature limits on a transitory basis without departing from the scope of the invention although, for enhanced economic and technical practicability of commercial applications, the average reaction bed temperature should desirably be within the preferred range indicated above, i.e. from about 100° C., most preferably from about 200° C. up to about 350° C. At higher temperatures, the suitability of the catalyst for use in the cyclic two-step process of the invention is diminished so that the overall efficiency of the process is adversely affected, and the cost thereof increased, at such less favorable operating conditions.

It should be noted that the active surface carbon formed in the practice of the invention is quite distinct from the inactive coke formed if the carbon monoxide decomposition is allowed to proceed beyond the maximum level of active surface carbon deposition. As indicated by the references to carbon deposition in the prior art description above, such inactive coke is known in the art as an undesired potential deposit on catalyst surfaces from carbonaceous feeds employed in various methanation operations. Such coke has essentially the reactivity of graphitic carbon. Its reaction with steam, for example, requires temperatures in the range of from about 600° C. to about 1000° C. This reaction, which is the well-known water gas reaction, produces CO and H₂ as its principal products. The active surface carbon of the present invention, on the other hand, reacts with steam at appreciably lower temperature levels to provide methane as its principal product in accordance with equation (5) above. While the prior art is concerned with the avoidance of the undesired deposition of inactive coke on catalytic surfaces, the present invention utilizes the deposition of active surface carbon, without formation of inactive coke, to produce methane by a novel, low-cost process as described herein.

The amount of active surface carbon deposited will depend upon the surface area of the disproportionation catalyst and the operating conditions employed. Relatively low temperatures and the shortest possible residence time tend to favor the formation of the active surface carbon. Under some circumstances, particularly at higher temperatures within the operable range or with a very long residence time, the presence of CO in the gaseous effluent denotes a relatively sharp demarcation point between the deposit of the desired active surface carbon and the undesired deposition or other formation of inactive coke on the surface of the catalyst. In determining the amount of active surface carbon that can be deposited on the catalyst, therefore, the point at which CO breakthrough occurs can be taken as a practical indicator of the maximum level of active surface carbon deposition. It will be understood, however, that said maximum level of deposition must be determined, for any particular embodiment, by the particular operating conditions employed, the specific catalyst utilized and the available surface area of the catalyst as applied in such embodiment.

The invention utilizes a catalyst capable of catalyzing the disproportionation of carbon monoxide. The transition metals including and to the left of nickel in the third row of the Periodic Table; including and to the left of rhodium in the fourth row thereof; and including and to the left of iridum in the fifth row thereof are capable of catalyzing said disproportionation. Preferred catalysts include nickel, cobalt, iron, ruthenium, rhenium and alloys thereof, with nickel and cobalt being most preferred on an overall technical-economic basis. For purposes hereof, it will be understood that the catalyst shall include the metallic form, the oxide form, or any other suitable form of the particular catalyst employed. As the active surface carbon will be deposited in a surface layer while assuring that the decomposition reaction does not proceed to the point of inactive coke formation, a high catalyst surface area is advantageous to achieve a high surface carbon loading, enhancing the economics of the process. The catalyst employed will preferably have a surface area of at least about 10 m² /gr, with surface areas of at least about 25 m² /gr being more preferred. In some embodiments, the catalyst may have an even higher surface area, i.e. of at least about 50 m² /gr., it being appreciated that such high surface areas contribute to the attractiveness of the invention on an overall technical and economic basis. It will also be appreciated that the catalyst will generally be employed in combination with catalyst support additives and/or binding agents to assure that the catalys has and maintains a desired combination of activity, capacity and stability for use in practical fixed or fluid bed commercial operations. It will also be understood that the surface area of the catalyst, as referred to herein, relates to the B.E.T. surface area of the catalyst composition measured after the combination of the catalyst with such additives or agents and after reduction of the catalyst to its active state.

For the economic production of methane in practical commercial operations, it is highly desirable that the catalyst be capable of use in the essentially two-step, cyclic, low-cost process of the invention without the need for regeneration following each reaction cycle. Furthermore, the catalyst should advantageously be capable of effective continued use in the cyclic two-step process of the invention over as long a cycle period as possible prior to regeneration to enhance the economic feasibility of the process in such commercial operations. For such cyclic operations that are inherently part of the economic attractiveness of the invention, the catalyst will, in particularly preferred embodiments, be employed essentially in its metal state and will be taken from especially preferred catalysts, including nickel, cobalt, ruthenium, rhenium and alloys thereof, with nickel and cobalt being most preferred on an overall technical-economic basis to enhance the cyclic feature inherent in the overall advantages of the two-step process that follows the feed gas pretreatment step of the invention. It will be understood by those skilled in the art that such catalysts, in their metal state, are not generally available in a totally pure form but may contain small amounts of oxygen. The especially preferred catalysts enhancing the cyclic, two-step methanation process of the invention will be substantially in the metal state rather than in oxide form. It will be noted that iron is not included among the especially preferred catalysts for practical commercial operation of the two-step, inherently, cyclic methanation process of the invention, since iron is considerably less reactive to CO in the initial disproportionation step that is the most preferred nickel and cobalt catalysts. In the active surface carbon conversion step, the iron is found to react with steam to form an oxide that may be inert or relatively inactive for carbon monoxide disproportionation depending on the valance state of the iron in said oxide. In addition to the generally less desirable nature of the use of catalysts in the oxide form, therefore, it may be necessary to convert the iron oxide catalyst to iron metal form as a separate and necessary additional step of the cyclic process. Such a requirement would, of course, change the process from one having, following the feed gas pretreatment for hydrogen removal, two essential chemistry steps. As indicated above, the economic and technical advantages of the inherently cyclic methanation process of the invention would not be realized in embodiments of commercial operations in which iron, in such oxide form, is employed as the disproportionation catalyst.

As indicated above, inert gases present in the pretreated carbon monoxide-containing feed gas stream following selective hydrogen removal, together with gases formed during carbon monoxide decomposition, are vented from the reaction zone in which a surface layer of active surface carbon is deposited on the disproportionation catalyst. As a result, the carbon values in the carbon monoxide that are to be converted to methane are separated from said inert gases inherently in the practice of the invention. Apart from the indicated pretreatment for hydrogen removal, no prior concentration of the carbon monoxide present in dilute carbon monoxide-containing gas streams, and no separation of said carbon monoxide from inert gases such as nitrogen and argon present in said gas streams, is required. It is such requirements and the cost thereof that effectively preclude the use of dilute carbon monoxide-containing gas streams in prior art methanation techniques. The present invention achieves, in effect, such concentration essentially without a cost penalty compared to alternative processes that utilize gas streams containing a relatively high proportion of carbon monoxide therein to avoid the necessity for employing a prohibitively costly cryogenic or other separation of inerts. The present invention is particularly advantageous and achieves a major advance in the art in permitting the methanation of dilute carbon monoxide-containing gas streams pretreated so as to be without appreciable quantities of hydrogen, but containing a relatively high proportion of inerts, e.g. the indicated gas streams containing from about 5% to about 50% by volume nitrogen.

The active surface carbon deposited on the catalyst, following the venting of inert gases therefrom, is contacted with steam or a steam-containing gas stream to convert said active surface carbon to methane and CO₂ in accordance with reaction (5) above. Reaction temperatures of from about 100° C. to about 400° C. may be employed, with conversion temperatures of from about 200° C. to about 350° C. being generally preferred. The conversion of active surface carbon by steam may be carried out at reaction pressures of from about 1 to about 100 atmospheres. By using high pressure steam for the active surface carbon conversion, the generation of a high pressure product gas stream is achieved without the need for expensive compression equipment and high energy consumption, further enhancing the economic attractiveness of the process. Thus, steam is the especially preferred reactant for conversion of the active surface carbon to methane in practical commercial operations in which the inherently cyclic, two-step methanation process of the invention is carried out for the methanation of CO-containing gas streams, pretreated for selective hydrogen removal, on an economically attractive basis.

The conversion of active surface carbon to methane can, less desirably, be accomplished by contacting the surface layer of said carbon with hydrogen or a hydrogen-containing gas stream under the operating conditions indicated above for conversion by steam. In this embodiment, methane is formed in accordance with the reaction:

    C*+2H.sub.2 →CH.sub.4.                              (7)

With the hydrogen requirements of reaction (7) being supplied from CO via the water shift reaction of reaction (2), the carbon efficiency of the process can be illustrated by the overall reaction (8) below that represents the total of reactions (2), (4) and (7) as performed in the practice of the present invention:

    4 CO+2H.sub.2 O→3 CO.sub.2 +CH.sub.4.               (8)

Thus, 4 moles of CO are again required for the production of one mole of methane in the stoichiometric relationship illustrated by reaction (8). Steam, however, is preferred for the active surface carbon conversion step because of the costs associated with the generation of hydrogen. The CO₂ formed in said conversion by steam can readily be separated from the methane, if desired, by well known commercially available techniques to provide a relatively pure, low-cost methane product. The Benfield aqueous alkaline scrubbing process and the Shell Sulfinol and Allied Chemical Selexol solvent extraction processes are examples of commercial techniques for removing carbon dioxide and other acid gases from gas streams.

The disproportionation catalyst will typically be mixed with a catalyst support additive or with binders to assure that the catalyst has a desired combination of activity, capacity and stability. In the absence of such additives and/or binders, nickel, for example, is relatively unstable and tends to agglomerate and sinter with resultant reduction of its surface area.

It is within the scope of the invention to employ any available support additive material capable of supporting and/or dispersing the catalyst, so as to prevent agglomeration and sintering thereof, to enhance the activity and capacity of the catalyst in continuous commercial operations. Such support additives will generally be employed in varying amounts ranging from about 0.1% to about 50% by weight of additive based on the weight of catalyst composition mixture of catalyst and additive. Examples of suitable additives are zirconia, thoria, alumina, silica and mixtures thereof, although various other materials, such as rare earth oxides, may be employed for the indicated catalyst support purposes. In particular embodiments, the additive is employed in an amount within the range of from about 3% to about 15% by weight based on the weight of the catalyst composition mixture. Zirconia, alumina and silica are preferred catalyst support additives with zirconia being generally most preferred.

It will be understood that various combinations of such support additive materials, with or without binding agents, may be employed to achieve desired support and/or dispersion of the disproportionation catalyst employed in particular embodiments of the subject methanation process. For example, it has been found advantageous to employ a combination of zirconia and alumina support additives. Each additive may preferably be employed in a an amount within the range of from about 3% to about 30% by weight of the catalyst composition mixture of catalyst and additive, with the combination being employed in an amount up to about 50% by weight based on the weight of said catalyst composition. As indicated above, nickel is the generally preferred catalyst, with the surface area of the catalyst being generally at least about 10 m² /gr, and preferably at least about 25 m² /gr, more preferably at least about 50 m² /gr. Binding agents, if employed, will generally be mixed with the catalyst composition in an amount within the range of from about 5% to about 40% by weight of such binding agent based on the total weight of the catalyst composition-binder mixture. Various binding agents known in the art may be employed in a conventional manner as will readily be appreciated by those skilled in the art. Boehmite alumina, a hydrous aluminum oxide, is a convenient readily available binder.

While various catalyst-support additive combinations suitable for the purposes of the cyclic methanation process may readily be determined by those skilled in the art, it has been found particularly convenient to employ a coprecipitated mixture of catalyst and catalyst support additive. Thermally stable coprecipitated catalysts useful for methanation reactions have heretofore been known in the art as evidenced, for example, by the Hansford U.S. Pat. No. 3,988,263 that relates to combinations of alumina with catalytic materials such as nickel. The catalyst support additive, in such embodiments, constitutes generally the hydroxide or carbonate form thereof coprecipitated with the hydroxide or carbonate of the catalyst material prior to the reduction of said catalyst hydroxide or carbonate to the active catalyst state. For purposes of the subject cyclic process, the catalyst should comprise from about 50% to about 99% of the catalyst composition mixture of catalyst and additive. Nickel and cobalt are preferred catalysts, with zirconia being the preferred catalyst support additive although it will be appreciated that alumina or other suitable support additives can also be employed.

While the invention necessarily includes two basic chemistry process steps, repeated on a cyclic basis, following pretreatment of the feed gas for hydrogen removal, it will be understood that various processing steps, or unit operation steps, may be carried out indicental to the essential features of the invention. Thus, it was noted above that pretreatment of the feed may be employed to remove sulfur impurities. Likewise, any methane formed during the carbon monoxide decomposition step as a result of the presence of residual amounts of hydrogen or water in the feed gas may be employed for heat generation purposes to enhance the overall economics of the process. In addition, by-product carbon dioxide formed during conversion of active surface carbon with steam in accordance with reaction (5) is separated from product methane by conventional techniques. It will be understood by those skilled in the art that various other processing steps incidental to the heart of the present invention may be employed in practical applications of the invention. Accordingly, small adjustments in reaction temperature may be made, as by heating or cooling the reaction zone, and a purge gas at a desired temperature, e.g. about 240° C., may be passed through said zone to achieve a desired cooling effect. As noted above, removal of hydrogen in the pretreatment step of the invention serves to alleviate temperature control problems that would exist if the feed gas to the disproportionation zone contained appreciable quantities of hydrogen. It will also be understood that, during repeated cycles of the cyclic, basically two-step methanation process of the invention, the disproportionation catalyst becomes coated with carbon that eventually reduces the efficiency of the catalyst to the point where catalyst regeneration becomes necessary or desirable. Oxidative regeneration can be employed to burn off said carbon so as to regenerate the catalyst for subsequent use in the cyclic, two-step methanation process of the invention. Such regeneration can be conveniently carried out in situ in the reaction zone. Other desirable means can also be employed to regenerate said catalyst on a periodic basis as required for effective catalyst utilization.

The following examples illustrate various aspects of the subject cyclic methanation process, and the desirable pretreatment of the feed gas for hydrogen removal purposes.

EXAMPLE 1

45.4 gr, 40 ml bulk of a nickel-zirconia coprecipitated catalyst composition having a weight ratio of 7 parts nickel per part of zirconia was loaded in a glass tube and was reduced at 400° C. in a stream of helium-hydrogen of approximately 10:1 ratio at a flow rate of 150 ml/min for 16 hours. The catalyst with said nickel in metal form had a surface area of approximately 100 m² /gr. The temperature was adjusted to about 200° C. and a mixture of helium and carbon monoxide in a 10:1 ratio, i.e. a dilute carbon monoxide stream, was passed through the catalyst bed at the rate of 830 ml/min for 20 minutes at one atmos pressure. The effluent was passed through solid absorbent chips to recover by-product carbon dioxide. The temperature was increased from 200° C. during this period. The absorbed CO₂ was found to measure 650 ml. No CO breaktrough in the effluent was observed.

The reactor temperature was adjusted to 250° C., and superheated steam in helium, at a ratio of 1:1, was passed through the bed at the rate of 360 ml/min for 13 minutes at one atmos. During the steam reaction period, the effluent was passed through the absorbent to collect additional by-product carbon dioxide. The helium carrier gas and product methane passed the absorbent zone and product methane was determined by use of vapor phase chromatographic techniques. 398 ml of additional by-product carbon dioxide were collected. The methane product was recovered in the amount of 298 ml out of a theoretical recovery of 400 ml, i.e. with an efficiency of 74%. Such conditions were observed during the 12th cycle, which was a representative cycle during the course of a 14-cycle application of the present invention in which the essential two steps thereof were repeated on a cyclic basis with no regeneration of the catalyst and with no necessity for employing any additional step for converting the catalyst from one form to another prior to commencing each succeeding cycle.

EXAMPLE 2

A nickel-zirconia catalyst composition having a 9/1 by weight nickel/zirconia ratio was heated in a 10/1 helium/hydrogen stream at 350° C. for 10 hours. After cooling in a helium stream, oxygen in helium in a 1/10 ratio was passed through the catalyst at room temperature. 18.6 g of catalyst was then loaded into a stainless steel pressure reactor and heated at 250° C. for 16 hours in a 10/1 helium/hydrogen mixture at a flow rate of 150 ml/min. The thus pre-stabilized and reduced catalyst with said nickel in metal form was the employed in the process of the invention by passing a 10/1 helium/carbon monoxide gas stream through the catalyst at a rate of 830 ml/min for 20 minutes, with the reactor temperature commencing at 210° C. 600 ml of carbon dioxide was collected in an absorber as in Example 1. No CO breakthrough in the effluent of the of the carbon monoxide decomposition reaction was observed.

The reactor was then heated to 275° C. and pressurized with helium to 210 psig. Superheated pure steam, without carrier gas, was introduced into the reactor at the rate of approximately 125 ml/min for a period of 11 minutes. The effluent gas was a dispersion containing product methane, by-product carbon dioxide and helium. 162 ml of additional CO₂ was recovered. Product methane was recovered in the amount of 226 ml, representing a 56.5% efficiency based on the theoretical recovery of 400 ml of said product. This run was carried out as a single cycle embodiment of the embodiment.

EXAMPLE 3

A catalyst composition as in Example 2, having a nickel to zirconia ratio of 9/1, was mixed with a binder in the weight ratio of 4 parts of said catalyst composition to 1 part of binder. Boehmite alumina, i.e. aluminum oxo-hydroxide, was employed as the binder. Upon mixing, the catalyst composition-binding agent paste was peptized in HNO₃, extruded and fired in air at 300° C. The resulting catalyst composition was reduced and stabilized as in Example 2 and was loaded into a stainless steel reactor and heated to 350° C. in a helium-hydrogen stream for 16 hours. With the reactor temperature adjusted to 220° C., CO was metered into a N₂ stream in the ratio of 1/9, i.e. producing a 10% CO-containing stream. This stream was introduced into the reactor at the rate of 1.1 l/min for 6 minutes. 315 ml of by-product CO₂ were recovered, with no CO breakthrough observed.

The reactor was pressurized at 210 psig with nitrogen, and superheated steam, as in Example 2, was introduced at the rate of 60 ml/min for 3 minutes with the reactor temperature commencing at 270° C. 655 ml of effluent gas was recovered, at which 143.5 ml was product methane. Theoretical recovery was 172.5 ml, so that the methanation efficiency was 83.2%. Such conditions were observed during the 4th cycle, which was a representative cycle in a 26 cycle run in which the two essential steps of the invention were repeated without catalyst regeneration and without any inclusion of an additional step to convert the catalyst from one form to another between any of said repeated cycles of the two step methanation process of the invention.

EXAMPLE 4

A cobalt-zirconia catalyst composition was prepared by dissolving the corresponding nitrates in water and adding an equivalent amount of sodium hydroxide in water to form the corresponding hydroxide precipitates that were filtered, washed and dried. A 9/1 weight ratio cobalt-zirconia coprecipitated catalyst composition prepared in this manner was charged, in a 30 gr amount, in a reactor tube and reduced by heating to 400° C. in a helium/hydrogen gas stream for 16 hours. The temperature of the reactor was adjusted to 229° C. and a helium/carbon monoxide mixture, containing 5% CO by volume, was passed over the catalyst with said cobalt in metal form for a period of 5 minutes. 134 ml of by-product CO₂ were measured.

With the reactor temperature adjusted to 247° C. at one atmo, a 30% mixture of superheated steam in helium was passed through the reactor at the rate of 220 ml/min for 5 minutes. A total of 56 ml of product methane was recovered, approaching 100% recovery. An active surface carbon loading of about 0.3% per weight of cobalt catalyst was observed, as opposed to nearly four times this catalyst loading capacity in the examples above utilizing nickel as the disproportation catalyst. The observations pertaining to this example were observed during the first cycle of a three cycle embodiment of the invention in the course of which the catalyst was not regenerated and was not converted from one form to another after each cycle and prior to repeating the two-step process in the next succeeding cycle.

EXAMPLE 5

A 10 g sample of a catalyst composition as in Example 3 was loaded into a stainless steel reaction vessel equipped with stainless steel shelves upon which the extruded catalyst materials were placed in a monolayer, said vessel being designed to allow good mixing of the reagent and carrier gases therewith and efficient reaction heat removal so as to insure good reaction temperature control. The reaction vessel was then loaded into a fluidized san bath and heated to 410° C. in a nitrogen/hydrogen stream of 20:1 volume ratio introduced at a rate of 1 l/min and maintained at 410° C. for 16 hours. After this catalyst reduction period, the catalyst was cycled 10 times at 290° C., with each cycle consisting of an exposure to a carbon monoxide-containing gas stream in order to deposit active surface carbon on the catalyst, followed by the injection of steam to convert said active surface carbon to a mixture of methane and carbon dioxide. These cycles were employed for the purpose of aging the catalyst prior to its use in the comparative studies set forth below and in Example 6.

The catalyst was then regenerated by burning off possible agglomerates of unreacted carbon with a stream containing 1% oxygen in nitrogen at 410° C., employing 1 l/min of said stream for a period of 10 hrs. The catalyst was again reduced as above following said regeneration to ensure removal of unreacted carbon.

The temperature of the reaction vessel was adjusted to 290° C., and a stream of nitrogen containing 2% carbon monoxide was introduced for a period of 7.5 minutes at the rate of 10 l/min. The first step reaction product gas was analyzed for carbon dioxide content, and a total of 232 ml of CO₂ was measured. The reaction vessel was pressurized to 150 psig with nitrogen following completion of the first reaction step, and was heated to 330° C., superheated steam at approximately 3 l(gas) per min. was introduced therein for 4 minutes. The effluent gas recovered was determined to contain 76 ml of methane. As the theoretical methane recovery in this steaming step was 116 ml, the methanation efficiency was 65.5%.

In the next identical cycle of the essentially two step process of the invention, carried out without regeneration or prior conversion of the catalyst, a total of 193 ml of carbon dioxide were measured in the active surface carbon deposition step, and 73 ml of product methane were recovered in the steaming, or active surface carbon conversion, step. Theoretical recovery was 96.5% so that the methanation efficiency was 75.6% in this second cycle.

EXAMPLE 6

The very same catalyst sample used in Example 5 was regenerated as before following completion of the second cycle of said Example 5, and the reaction vessel temperature was adjusted to 450° C. The cyclic process was then carried out as in Example 5 but with both steps carried out at 450° C. In the first process cycle at this higher temperature, 421 ml of carbon dioxide were measured in the first, or active surface carbon deposition, step, and only 7 ml of methane were measured in the second, or active surface carbon conversion, step. Thus, the methanation efficiency was found to be only 3.3%.

In a second identical processing cycle at said 450° C., 490 ml of carbon dioxide were measured in the active surface carbon deposition step, and only 7 ml of methane were recovered in the active surface carbon conversion step. Methanation efficiency in the second cycle was 2.8%.

In a third identical processing cycle, 514 ml of carbon dioxide were measured, and only 4 ml of methane were produced. The methanation efficiency of the third cycle at 450° C. was thus only 1.5%.

EXAMPLE 7

The illustrative embodiments of the cyclic methanation process of Examples 1-6 above did not utilize feed streams having appreciable quantities of hydrogen therein. Industrial waste streams do exist, however, that contain such quantities of hydrogen together with dilute concentrations of CO suitable for methanation by the cyclic process described above. Carbon black tail gas has been cited as one example of such an industrial waste stream suitable for CO recovery by means of the invention. Such a carbon black tail gas to be treated by means of the present invention is found to contain, on a pound moles per hour basis, 16.0 moles of CO, 16.0 moles of hydrogen, 4.0 moles of CO₂, 63.5 moles of N₂ and 0.5 moles of H₂ O, at 300° F. and 15 psia. The tail gas is fed to a partial oxidation combustion furnace maintained at about 1060° F. and 2 atmos. Air is fed at the rate of 50.8 lb moles per hour to the combustion furnace at 100° F. and 1 atmos, thus introducing 10.7 lb. moles of oxygen and 40.1 lb. moles of nitrogen to the combustion furnace. A product stream containing, on said pound moles per hour basis, 10.7 moles of CO, appreciably no hydrogen, 9.3 moles of CO₂, 103.6 moles of nitrogen, and 16.5 moles of water, for a total of 140.1 moles. Said stream is passed to a dehydration zone for removal of the water content thereof, by partial condensation and glycol scrubbing, prior to being passed over the disproportionation catalyst for deposition of active surface carbon thereon. In this example, the amount of air employed was selected so that it was sufficient to oxidize essentially all of the hydrogen and some, i.e. up to about 1/3, of the CO present in said typical carbon black tail gas composition. The resulting partial pressure of this tail gas-air mixture and the desired operating pressure of the furnace determine the optimum flame temperature, i.e. the partial oxidation reaction temperature, at which the desired selective oxidation of hydrogen can be carried out at a sufficiently fast rate for reasonable furnace design without crossing into the explosive range for such mixture. It will be appreciated by those skilled in the art that the partial pressure of a gaseous species is obtained as the mole fraction of said species in a gaseous mixture multiplied by the total pressure of the gaseous mixture. In this instance, the total partial pressure of hydrogen and oxygen in the reaction mixture is obtained from the mole fraction of 10.7 moles of O₂ and 16.0 moles of H₂, or a total of 26.7 moles of O₂ and H₂ in a reaction mixture having a total composition of 150.8 moles, i.e. 100.0 moles of tail gas and 50.8 moles of air. At the desired operating pressure of 2 atmos., the total partial pressure of the hydrogen and oxygen is found to be 269.1 mm Hg. As determined on said FIG. 1 and FIG. 13 of the Lewis and Vonelbe text, referred to above and incorporated herein by reference, it will be seen that the optimum temperature for said partial oxidation reaction is in the order of about 570° C., or about 1060° F. as indicated above. It will be appreciated that lower operating temperatures within the non-explosive region as shown in said Figures can also be employed, it being noted that such lower temperatures result in lower reaction rates as shown on said FIG. 13.

For practical commercial applications, it would be highly desirable to employ catalyst compositions having carbon loading capacities in excess of 0.8% together with desired stability to enhance the economic advantages obtainable in fluid bed or fixed bed applications of the methanation process herein disclosed and claimed. It will be appreciated that various catalyst compositions can be formulated that, because of the relatively low proportion of active catalyst and/or the lack of sufficient available catalyst surface area, are not adequate to achieve the methanation efficiencies capable of being achieved in the practice of the invention and to which the invention is reasonably limited as herein indicated. It will also be appreciated that the effective surface area of any given catalyst compositing may tend to decline over the course of long term, continuous operations while, nevertheless, achieving the significant advance in the art obtinable by the process of the invention, particularly in the utilization of dilute carbon monoxide-containing gas streams.

The combined feed gas pretreatment-cyclic methanation process of the invention, as herein disclosed and claimed, represents a highly desirable advance in the field of methanation. It permits the production of high-Btu, pipeline-standard methane from industrial by-streams of dilute carbon monoxide not suitable for methanation by conventional methods. Many million tons of dilute by-product CO are flared each year by such basic industries as pig iron production in blast furnaces, gray iron casting, petroleum cracking, and the manufacture of carbon black. Furthermore, dilute CO-containing gas streams are available from coal gasification with air and from in-situ or underground coal gasification operations. When the CO-containing gas stream suitable for methanation by the subject cyclic methanation proves also contains appreciable amounts of hydrogen, as in the use of carbon black tail gas, the selective removal of hydrogen by the partial oxidation step of the invention significantly enhances the overall methanation operation by avoiding the generally undesired formation of appreciable amounts of methane during the active surface carbon deposition step of the cyclic process without the necessity for employing methanation catalyst in a pretreatment step prior to said cyclic process.

The overall process of the invention represents an attractive technical and economic alternative to CO concentration by cryogenic or absorption techniques prior to methanation or to the discharge of dilute CO-containing gas streams to waste. As shown above, the process enables the carbon monoxide in dilute CO-containing gas streams also containing appreciable quantities of hydrogen to be converted and/or separated from inert gases without the need for the costly pretreatment to concentrate and separate CO that has precluded the commercial production of methane from dilute CO-containing gas streams. The subject invention can thus be effectively utilized for the production of methane from such heretofore unsuitable sources of CO, such as carbon black tail gas or other gases containing appreciable amounts of hydrogen as well as from the effluent from the underground gasification of coal with air, the effluent from blast furnace operations, the raw synthesis gas from the oxygen-blown gasification of coal and other such CO-containing gas streams. The product methane is obtained as a low-cost, relatively pure product, capable of being produced at pipeline pressures, without reliance upon hydrogen as a reactant, with the subject process appearing to be competitive with large-scale SNG production by conventional coal gasification means. While the process is directed to the production of methane, it should also be noted in passing that various other products, such as ethane or other specific organic compounds, may conceivably be produced in various particular embodiments of the invention.

The production of methane by means of the subject invention provides a practical means for utilizing hydrogen dilute CO-containing gas streams, and thus for reducing the waste of CO and for recovering and reusing such CO from industrial exhaust gases to produce low-cost, high purity methane as a replacement for natural gas. The invention constitutes, therefore, a significant advance of major importance in meeting the energy requirements of industrial societies throughout the world. 

I claim:
 1. A cyclic process for the production of methane from carbon monoxide-containing gas streams also containing appreciable quantities of hydrogen therein, said processs comprising:(a) contacting a carbon monoxide and hydrogen-containing gas stream with air in a partial oxidation reaction zone, said air being employed in an amount such that, at the reaction temperature and pressure employed, the total partial pressure of hydrogen and oxygen in the reaction mixture is within the limits for non-explosive reaction of homogeneous mixtures of hydrogen and oxygen at said reaction conditions, thereby resulting in the selective oxidation of said hydrogen in preference to the carbon monoxide content of the reaction mixture; (b) passing the resulting carbon monoxide-containing gas stream having hydrogen removed therefrom to a dehydration zone for the removal of water vapor therefrom; (c) passing the carbon monoxide-containing gas stream removed from said dehydration zone over a catalyst present in a metal state and capable of catalyzing the disproportionation of carbon monoxide at a pressure of from about 1 to about 100 atmos and a temperature of from about 100° C. to about 350° C., said carbon monoxide thereby being decomposed to form carbon dioxide and an active surface carbon that is deposited on said catalyst, which is taken from the group consisting of nickel, cobalt, ruthenium, thenium, and alloys thereof, said gas being passed over the catalyst for a time sufficient to deposit a surface layer of active surface carbon on the catalyst essentially without the subsequent formation of inactive coke thereon, the prior partial oxidation reaction and dehydration step serving to minimize methanation formation during said active surface carbon deposition; (d) contacting said layer of active surface carbon deposited on said catalyst present in a metal state with steam or a steam-containing gas stream at a pressure of from about 1 to about 100 atmos and a temperature of from about 100° C. to about 400° C., thereby converting said active surface carbon to methane and carbon dioxide, said methane being at least about 50% of the stoichiometric amount, the carbon thus recovered in the form of methane being at least about 12.5% of the carbon in said carbon monoxide decomposed upon contact with said disproportionation catalyst; and (e) passing additional carbon monoxide-containing gas, pretreated as in steps (a) and (b) above over said catalyst from step (d) and repeating said steps (c) and (d) on a two step cyclic basis,whereby relatively pure methane can conveniently be produced from CO-containing gas streams on a cyclic two-step basis without the necessity for the prior concentration of said carbon monoxide and/or the separation thereof from inert gases or for converting the catalyst from one form to another between said cycles, the selective removal of hydrogen from the feed gas enhancing the active carbon deposition reaction and the overall efficiency of the methanation reaction.
 2. The process of claim 1 in which said gas stream contains from about 5% to about 50% by volume carbon monoxide and at least about 5% by volume nitrogen.
 3. The process of claim 1 in which said catalyst comprises nickel.
 4. The process of claim 1 in which said catalyst is mixed with a catalyst support additive in the amount of from about 0.1 to about 50% by weight based on the weight of said catalyst composition mixture of catalyst and additive, said catalyst having a surface area of at least about 10 m² /gr.
 5. The process of claim 4 in which said catalyst comprises nickel and said additive comprises zirconia.
 6. The process of claim 1 in which said partial oxidation reaction is carried out at a temperature of from about 540° C. to about 575° C.
 7. The process of claim 1 in which said partial oxidation reaction is carried out at a reaction pressure of from about one to about two atmos.
 8. The process of claim 2 in which said gas stream fed to said partial oxidation reaction zone contains from about 5% to about 20% by volume hydrogen.
 9. The process of claim 8 in which said gas stream fed to the partial oxidation reaction zone comprises carbon black tail gas.
 10. The process of claim 1 in which said carbon monoxide and hydrogen-containing gas stream is contacted with air in a fluidized bed furnace reaction zone, said fluidized bed serving to dampen localized temperature variations and thus ensure against conditions in the explosive range for said reaction mixtures containing oxygen, hydrogen and carbon monoxide therein.
 11. The process of claim 1 in which said carbon monoxide and hydrogen-containing gas stream is contacted with air in a gas furnace partial oxidation reaction zone.
 12. The process of claim 1 in which said carbon monoxide and hydrogen-containing gas stream is contacted with air in a plug flow tubular furnace partial oxidation reaction zone.
 13. The process of claim 1 in which residual amounts of hydrogen and water present in said carbon monoxide-containing gas stream contacting said disproportionation catalyst being converted to methane, said methane being vented from the catalyst having said surface layer of active surface carbon deposited thereon together with said carbon dioxide and inert gases present in the gas stream.
 14. The process of claim 13 and including subjecting said vented methane to combustion in a combustion zone for heat generation purposes.
 15. The process of claim 8 in which said catalyst comprises nickel.
 16. The process of claim 15 in which said catalyst has a surface area of at least about 25 m² /gr.
 17. The process of claim 16 in which said carbon monoxide and hydrogen-containing gas stream comprises carbon black tail gas and said partial oxidation reaction is carried out at a temperature of from about 540° C. to about 575° C. 